Manufacture of aluminum chlorid.



A. MUD. MUAFEE.

MANUPATURE OP ALUMINUM UHLRID.

APPLwA'rIou FILED rsu. 1s, 1914.

1,099,096, Patented June 2, 1914.

:Srccrs: qsgg: r

i E j l Y ,e0 jf if Y y I4 i fV anvwoz ALLIER MUDUFFIE MCAFEE, OF BAYONNE, NEW JERSEY.

MANUFACTURE 0F ALUMINUM CHLORID.

Specification of Letters Patent.

Patented J une 2, 1914.

Application led February 12, 1914. Serial No. 818,285.

To all whom it may concern Be it known that I, ALMER MCDUFFIE Mo- AFEE, a citizen of the United States, residing at Bayonne, in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in the Manufacture of Aluminum Chlorid, of which the following is a specification.

This invention relates to the manufacture of aluminum chlorid; and it comprises a method of utilizing certain oily residual materials formed inthe treatment of oils with aluminum chlorid or with substances capable of forming aluminum chlorid, such method comprising removing oil from such residues, bringing the oil-freed material to a high temperature and contacting therewith chlorin or chlorin-containing gas, to recover aluminum chlorid; all as more fully hereinafter set forth and as claimed.

Aluminum chlorid, and substances capable of forming aluminum chlorid, may be employed in treatin various oils to produce useful catalytic e ects therein; and particularly in treating mineral oils. I have elsewhere described and claimed one such process, for example, wherein I distil crude pet-roleum, petroleum distillates or residues in the presence of aluminum chlorid, refluxing unchanged oil back into the still, and producing a conversion into gasolene or gasolene and kerosene, as the case may be. Or in lieu of using' aluminum chlorid in treating oils, I may employ substances capable of forming aluminum c lorid, such as hydrochloric acid or chlorin together with alumina (bauxite) or metallic aluminum. In another such process, I warm lubricating oils with aluminum chlorid to produce a decolorizing and purifying effect on such oils, and to convert unsaturated compounds therein into saturated. In the stated processes, and in other processes of treating mineral and other oils with aluminum chlorid, the aluminum chlorid after a time loses its activity and forms a sludge or coky residue as the case may be, which, usually, practically completely separates out of the 011 on cooling. This residue or sludge probably contains much or most of the aluminum chlorid as such but in a state of combination with other components of such a residue. On heatin such a residue, the contained aluminum c lorid does not volatilize readily, in fact, the material may be heated above the vention, therefore, I take a slud normal volatilizing tempera-ture of aluminum chlorid without any great formation of vapors of that substance. I have found, however, that by treating these residues While hot with a comparatively small amount of chlorin, the aluminum chlorid is released from its state of combination (if such it be), and a copious formation of aluminum chlo rid vapors takes place. In the prescrit inor ook residue of the character descri d which7 generally contains a considerable amount of adhering oil, and I first substantially free it from this oil. The oil may amount to 50 per cent. or more of the residue and can be recovered by extracting the residue with gasolene or other solvent; but as a rule, I find it more advantageous to remove the oil in another manner. By heatin the residue gradually, the adhering oil Eecomes more Huid, and much or most of it may then be drained ofi' and recovered. In cases where aluminum chlorid has been used in treating oil in a still and the body of oil is finally cooled therein to cause a separation of the oil from `the residue, after removal of such oil body the residue may be reheated without removal from the still, and oil liberated by the reheating drained or sucked olf in any convenient manner. Or, the residue may be removed from the still and reheated in another vessel. Residual organic bodies, including any small amount of oil which may have remained, are then carbonized by raising the heat. After carbonization, the residue is free of organic impurities. In heating, air` andV moisture should be carefully excluded. DuringV the carbonization there is usually some evolution of hydrochloric acid gas. The acid gas may be led ofi' and collected or may be led into another charge in a further advanced state of treatment, as hereinafter explained. Up to the point of complete carbonization, and somewhat beyond it, no particular loss of aluminum chlorid need be feared. Even after a complete removal of the oil, the residue on heating generally softens and takes on an Vasphalt-like consistency prior to complete carbonization. In carbonization the material may be brought to a. low red heat. On now bringin a current of chlorin into oontact with this hot material a copious evolution of fumes of aluminum chlorid is produced. These fumes may be led oi and condensed in a suitable receiver. W'hen the formation of aluminum chlorid vapors ceases, the introduction of chlorin may be discontinued. The residue finally remainin in the apparatus is mostly carbon.

oil-treating processes where aluminum chlorid is employed, presence of moisture in the oil is carefully avoided, as water breaks up the chlorid with formation of alumina, but in the event of moisture being present er gaining access during or after treatment of the oil with the chlorid and alumina occurring in the residue to be treated under the present invention, this alumina will be converted into aluminum chlorid by the con joint action of the carbon and chlorin. Where it is desired to add to the amount of aluminum chlorid, a little bauxite or other form of alumina may be conveniently mixed with the carbonaceous residue prior to the introduction of ehlorin. The carbon of the residue will serve in connection with the chlorin to reduce a further quantity of aluminum c ilorid from such bauxite.

In lieu of using chlorin, other chlorincontaining bodies, such as dry HC1 gas, may be used. An advantageous and economical operation is afforded by leading the hydro chloric acid gas formed in heating or cai'- bonizing one charge into another charge which has already been carbonized und is ready for the production of aluminum chlorid. The hydrochloric acid gas may be used alone or in admixture with chlorin.

The removal of the oil,the carbonizing and the recovery of aluminum chlorid need not, of course, be effected in one and the same apparatus, but each stage may be, and often advantageously is, performed in a separate vessel under appropriate conditions. This has, for example, the advantage that the aluminum chlorid forming apparatus need not be cooled in introducing a fresh charge. It is of course also possible to perform the operations of the present invention suceessively on an advancing column or stream of material passing more or less continuously through a suitable apparatus. In using two retorts in series, for example, the material may be merely heated in the iirst to the temperature necessary to' disengage oil. while the second retort is at a higher heatgwa heat sufficient to carbonize or to form aluminum chlorid. Any hydrochloric arid gas given oif during the oil liberation in the tirst retort may be led into the -second retort to assist in liberating aluminum chlorid. The heated, oil-freed material from the lirst retort may be dumped or led into the second retort and there carbonized and tinl aluminum chlorid recovered.

In the described operation any suitable type of apparatus may he used; as for oxample, clay gas retort vertically placed.

a structure omhmlying an ordinary i tort should have connections for draining off the oil set free on heating, for discharging vapors and gases, for introducing chlorin and for leading the aluminum chlorid set free and produced to a place of collection. Any ordinary heating means may be Yadopted but oil firing or gas firing is convenient.

1n the accompanying illustration I have shown one form of apparatus of the many adapted foi` use in the described operation.

In the view, which is a vertical section, element 1 is a retort which may be of clay, silicious material, etc., and is held within a casing or furnace chamber 2, fired at 3 by any suitable means (not shown). Above the retort is an extension 4, having outlet conduit 5 for aluminum chlorid vapors and closed by arch G, which may carry, as shown, hell-and-cone feed 7. The bell and feed device may be of iron, steel or bronze; but is best protected by a clay or like covering.

At the bottom, the retort carries a tapered Y metal continuation 8 (also preferably lined) with pivoted door 9 for dumping exhausted material. Outlet conduit l() may be provided for drainin off oil and inlet conduit 1i for the intro uction of chlorin. The conduit for aluminum chlorid vapors (5) extends past a pair of chambers, 12 and 13, closed below b bottoms, 14 and 15. As shown, these cfiambers are provided with doors 1G and 17 and with upper removable closures i8 and 19. Outlet Q0 may be provided for leading off gases.

The use of this structure is obvious from the foregoing. Aluminum chlorid residues arising from any treatment of any oil or any fat with aluminum chlorid or with materials forming aluminum chlorid ma be introduced into chamber 1 by means o the cone feed 7. The heat through 3 is then adjusted so as to warm up t e residues suiiieiently to cause the oil to flow down. It is tapped off at l0. The heat is 'now raised until the residual material is thoroughly carbonized, until all the volatile matters which can be expelled by pyrolytic decomposition of hydrocarbons, etc., are expelled and until the mass is thoroughly charred. During this operation the heat may be raised until the mass becomes red hot without fear of loss of aluminum chlorid. After the mass is charred, chlorin is led in through 11 and aluminum chlorid vapors pass out through condensing for the most part in chamber l2. Chamber 121 receives a further condensate ot aluminum chlorid. Uncondensed gases pass away through Q0. instead of rhlorin, hydrochloric acid or other chlorinrontaining gas or vapor may be led in through Vl l. When the expulsion of aluminum ehiorid is finished, the residual mass may he dumped by opening 9. Vl't is better 'l'his ri to do this rather than leave it and put another charge of fresh material on to of it, since the porous residual carbon will take up oil. The process may now be repeated.

While for the sake of simplicity of illustration but one retort is shown, of course a plurality of such retorts operating in parallel or in series may be used. Other condensing arrangements may be substituted for those shown, but the chambers shown are simple and convenient.

In case it is desired to form new aluminum chlorid in addition to that to be recovered, this can be easil accomplished, as stated, by mixing a litt e bauxite, or other form of alumina, with the residue prior to placing in the retort. The addition of aluminum chips or shavings is more expensive but can be practised. There is usually enough-carbon in the carbonized mass to convert considerable alumina.

What I claim is l. The process of recovering aluminum f chlorid from oily residues which comprises removing oil from such residues, heating to carbonize and contacting chlorin therewith.

2. The process of recovering aluminum chlorid from oily residues which comprises heating such residue to a carbonizing temperature and contacting chlorin therewith.

3. The process of recovering aluminum chlorid from oily residues which comprises removing oil from such residues, heating to carbonize and contacting a gas containing chlorin therewith.

4. The process of recovering aluminum chlorid from oily residues which comprises heating such residue to a carbonizing temperature and contacting a gas containing chlorin therewith.

5. The process of recovering aluminum chlorid from the residues formed in the treatment of petroleum oils therewith which comprises heating such residues to remove oil, heating the oil-freed residue to carbonize organic matter and treating the carbonized residues with a gas containing chlorin.

6. The process of recovering aluminum chlorid from the residues formed in the treatment of petroleum oils therewith which comprises heating such residues to remove oil, heating the oil-freed residue to carbonize organic matter and treating the carbonized residues with chlorin.

l7. The process of recovering aluminum chlorid from residues formed in the treatment of petroleum oils therewith which comprises heating such a residue to a temperature at which contained oil will drain olif', draining o such oil, raising the temperature of the material to a red heat and contacting chlorid with the hot material.

In testimony whereof, I aix my signature in the presence of two subscribing witnesses.

ALMER MCDUFFIE MCAFEE.

Witnesses:

F. J. K. HAUxHUns'r, J ULLA M. MCCABE.

lIt is hereby eertied that in Let-ters Patent No. 1,099,096, granted June 2, 1914, .upon the applieatiou of Almer McDuie McAfee, or Bayonne, New Jersey, for an improvement in The Manufacture of Aluminum Chlorid, errors appearV in the printed specification requiring correction as follows: Page 3, line 61, for the word ehlorid'read Mori/; andthe .name of .the first-mentioned witness to the signature of the patentee et the end of the specification, for F. J. K. Hauxhurst`rea.d T. S. E Ham/wm,- and that the said Laders Patent simula b'e read with-these eorretions therein that the same may conform to vthe record of the case in the Patent Oce. 4 l

Signed and sealed this 23rd day of June, AND., 1914,

i Y R. F. WHITEHEAD,

Acting Uommissoner of Patents. 

